Unsaturated organic compounds



Unlwd tates PatentiOf UNSATURATED ORGANIC COMPOUNDS Comer DrakeShacklett, Roselle, N. .l., assignor to E. I. duPont de Nemours andCompany, Wilmington, Del., a corporation of Delaware No Drawing.Application November 2, 1953, Serial No. 389,873

19 Claims. (Cl. 260-482) Still more particularly it relates toN-substituted amides of unsubstituted acrylic acid andalpha-hydrocarbon-substituted acrylic acid containing a betaine groupand certain of their derivatives. The invention further relates toprocesses of preparing such compounds. b

An object of this invention is to provide a new class of ethylenicallyunsaturated amides which are capable of addition-polymerization. Anothedobject is to provide such compounds which form addition polymers capableof forming hard films. A related object is ,to provide such compoundswhich can be readily polymerized to form colloids having hydrophilicproperties that are useful as gelatin substitutes. Yet another object isto provide a new class of ethylenically unsaturated amides containing abetaine group. A further object is to provide processes for preparingsuch amides from available chemical compounds. Still other objects willbe apparent from the following description of the invention.

The above objects are accomplished in accordance with the presentinvention which in its broader aspects pro-' vides N-substituted amidesof acrylic acid and alphahydrocarbon-substituted acids of the generalformula:

I I CH2=CC ONH-R1NRG o o- (I) where R is a member taken from the groupconsisting of hydrogen, alkyl radicals of l to 3 carbon atoms, phenyl,and cyclohexyl; R1 is a divalent saturated aliphatic hydrocarbon radicalof not more than 6 carbon atoms, R is a divalent saturated aliphatichydrocarbon radical of 1 to 4 carbon atoms; and R2 and R3 are the sameor diiferent alkyl radicals or 1 to 3 carbon atoms; preferably R1 is apolymethylene radical of 2 to 6 carbon atoms.

Amides of the type covered by Formula I wherein R is a divalent,saturated, aliphatic hydrocarbon radical having the configurationCHR"CHR"'- in which R" and R may be hydrogen, methyl or ethyl and theother symbols have the values assigned above can be made in accordancewith one aspect of this invention by the reaction of (1) adialkylaminoalkyl-acrylamide or cit-hydrocarbon substituted-acrylamidehaving a hydrogen atom attached to the amido nitrogen atom with (2) aS-lactone, preferably in the presence of an inert liquid diluent whichmay be a solvent for said reactants, at a temperature from 20 to 40 C.and preferably between 0 C. and 20 C. in the substantial absence ofwater including water vapor. The precipitated amide is then recoveredunder moisture-free conditions. Suitable inert diluents include diethylether, acetone, methylethyl ketone, tetrahydrofuran and dioxane.

Certain derivatives of amides of the type covered by general Formula Iwherein R is a divalent, saturated, aliphatic hydrocarbon radical havingthe configuration CHR4 where R4 is hydrogen, methyl, ethyl, propyl orisopropyl, and the other symbols have the values assigned above can bemade by reacting (a) a dialkylaminoalkyl-acrylamide ora-hydrocarbon-substitutedacrylamide having a hydrogen atom attached tothe amido nitrogen atom with (b) a lower alkyl ester of ana-halogen-substituted fatty acid preferably in the presence of an inertliquid diluent of the type described above at a temperature from 20 C.to 60 C. and preferably 20 C. to 30 C. When temperatures above 60 C. areused it is best to add an addition polymerization inhibitor to preventpolymerization. The resulting derivatives of the betaines have thegeneral formula:

'wherein R5 may be alkyl of l to 4 carbon atoms e. g. methyl, ethyl,propyl, isopropyl or n-butyl and X is Cl:

Bror I- and the other symbols have the values assigned previously. Theymay be removed from the reaction mixture by filtration and may then besubjected to hydrolysis in aqueous solutions in the presence of asuitable base. This hydrolysis reaction can be carried out at any time.For example, in the preparation of polymers containing betaine groupsthis latter step may be carried out before or after the polymerizationreaction.

The betaines and betaine derivatives of Formulae I and II arenon-resinous solid compounds which can be isolated in substantially purestate. At normal temperatures they are crystalline and soluble in water,lower aliphatic alcohols, e. g., methanol and ethanol, and polar organicsolvents, e. g., dimethylformamide and, in general, they are insolublein non-polar organic liquids. The

compounds are useful in the preparation of various other organiccompounds and are particularly useful for the preparation of polymersand copolymers by an additionpolymerization reaction. The individualcompounds or mixtures of two or more of them can be polymerized to formpolymers or copolymers, or they may be admixed with a still dillerentethylenically unsaturated compound,

e. g., acrylic or methacrylic acid or their esters, a vinyl EXAMPLE IBetaincs from propiolactone and N-dialkylaminoalkylacrylamides 0ralpha-substituted-acrylamides To a stirred ice-cooled solution of onemolar part of the respective aminoamide given in Table I below,dissolved in 212 parts of diethyl ether, 238 parts of acetone, or 242parts of methylethyl ketone, there is added, dropwise during a period of1.5 to 2 hours, one molar part of propiolactone dissolved in of thequantity of the same solvent employed for the aminoamide. The mixture isallowed to stand for 24 hours and the resulting crystallinebetaine-amide is removed by filtration in a moisture-free atmosphere,washed several times with fresh portions of acetone or diethylether anddried in the absence of moist air, preferably in vacuo. The respectivecompounds are Patented Jan. 15, 1957 recovered in the yields listed andhave the names and EXAMPLE 11 properties listed it] the following table:

TABLE I Betazne derlvatzves prepared from N-dzalkylammoalkylacrylamzdesor a-substztuted-acrylamzdes and halogen- Aminoamide Betaine-Amide.Yield, Melting lower aliphatic acld 35!? Percent Point,C.

To a solution of one molar partof the respective amino-3-MGtha1PY1ME1dQPYOPY1' 9 l 95 11541 amide given in Table II dissolvedin 396 parts of acetone dimethylamine. propyl-N,l\ -d1m e t hygl-fl-amino-propionate 7 there was added 1.1 molar part of therespective haloetaine. 1 1 2-Methaerylamidoethyl- N, 2-Methaerylamido-95 18'-.0S.5 10 deflated as hsted Said f lf 11 d et yle y parts ofacetone and the resulting mixture was. stirred fl-amlnopro pionate mthoroughly and allowed to stand for a period of from3-Aorylamidopropyldi- N, 3-Acrylamido-pro- 83 118-121 methylammfl py1N,N dh.nethy1 B several hears to several days, denendmg on the rapidamino-propionate he- 15 ity of precipitation of the crystallinederivative. When In l I 2 Ac1.V;amm0ethy1di F ziewmmmoethyl, 111412.precipitation was complete the white crystalline product mfithylamme- Y"5-?-' was removed by filtration in a moisture-free atmosphere,

mmo-proplonate hetaine. 1 washed with several portions of fresh solventand dried 1111 a moisture-free atmosphere, preferably in vacuo.

TABLE II Aminoamide Halogenated Ester Betaine Derivative Yield, MeltingPercent Point, C. x

. r 2-1Vletl1aerylamid0ethyldimethylamine" MethylChloroecetageCarbemethoxymethylB-Methaerylamido- 75 155-157 I ethyl DlmethylammonlumChloride. Do Ethyl Chloroaeetate Carboethoxymethyl z-Methacrylamido- 75126-127.

- ethylDimethylammonium Chloride. Do Methyl BromoaeetateCarbomethoxymethyl2-Metl1aerylamido- 84 147-148 ethyl DimethylammoniumBromide. Do Ethyl Bromoaoetate Carboethoxymethyl 2-'\/lethacrylamid0- 94106-107 ethyl Dimethylammonium Bromide. Do Methyl IodoacetateCarbomethoxymethyl2-Methacrylamide- 75 106-107 ethyl DimethylammoniumIodide. Do Ethy1I0doaeetate Garhoethoxymethyl 2-Methaerylamid0- 34 92-93ethyl Dimethylammonium Iodide. D0 Ethyl a-Bromopropionate-..l-Carboethoxyethyl 2-Methaerylamido- 75 110-111 ethyl DimethylammoniumBromide. D0 Methyl a-Iodopropxonatcl-Carbomethoxyethyl2-Methae1'ylamid0- 63 114-114.5

ethyl Dimethylammonium Iodide. Z-Methacrylamidoethyl diethylamme MethylChloroaeetate Carbomethoxymethyl 2-Methanrylamid0- 27 148-149 (deeJethyl Diethylummonium Chloride. D0 MethylBromoaeetateCarbomethoxymethylZ-Methaerylamido- 83 134-135 ethyl DiethylammoniumBromide. Do Ethyl Bremoaeetate Carhoethoxymethyl 2-1\-Iethacrylamid0-121-122 ethyl Diethylammonium Bromide. Do Methyl IodoaeetateCarbomethoxymethyl2-Methaerylamid0- 97-98 ethyl Diethylammonium Iodide.Do Ethyl Iod0aeetate- Carboethoxymethyl 2-1Vletl1aerylamid0- 85 11 1-115ethyl Diethylammonium Iodide. v 3-MethaerylamidopropyldimethylamineMethyl Chloroacetate Carbomethoxymethylfi-Methaerylamido- 73 129-130propyl Dimethylammonimn Chloride. Do Ethyl ChloroaeetateCarboethoxymethyl advlothacrylamido- 147-118 propyl DimethylammoniiunChloride. Do Methyl Bromoaeetate Carbomethoxymethyl3-1Iethacrylamid0- 92131-132 propyl Dimethylammonium Bromide. Do Ethyl BromoacetateCarboethoxymethyl 3-Mcthaerylamido- 86 -126 propyl DimethylammoniumBromide. Do Methyl Iodoaeetate Carbomethoxymethyl3-Methaerylazmdo- 91123-124 propyl Dimethylammoniumlodlde. Ethyl IodoaeetateGarboethoxymethyl B-Methaerylamido- 70 96-97 propyl DimethylammoniumIodidc. Ethylu-Bromopropxonate... l-Carhnethoxyethyl 3-Methaerylamid0-56 93-94 propyl Dimethylammonium Bromide. Methyl a-Iodoprop1onate.l-carbomethoxyethyl S-ldethaerylamido- 03 110-120 propylDimethylammoninm Iod1de. a-lvlethaerylamidopropyl diethylamme MethylBromoaeet-ate Carbomethoxymethyl3-Methaerylam1do- 91 1675-168 propylDiethylammonium Bromide. Ethyl Bromoacetate Carboethoxymethyl3-Methacrylamid0- 70 114-115 I propyl Diethylammonium Bromide MethylIodoaeetate Carbomethoxymethyl3-Methacrylamldo- 81 159-160 propylDiethylammonium Iodide. Ethyllodoacetate Carboethoxymethyl3-Methaerylamido- 85 129-130 I propyl Diethylammonium Iodide.

Methyl Chloroacetate Carbomethoxymethyl 2-Acrylamidoethyl 96 -150 (doe)Dimethylemmonium Chloride. Methyl Bromoaoetate Carbomethoxymethyl2-Acrylamidoethyl 88 129-130 Dimethylammonimn Bromide. EthylBromoacetate Carboethoxymethyl 2-Acrylam1doethyl 48 75-76Dimethylammonium Bromide. Ethyl Iodoaeetate Oarboethoxymethyl2-Acrylamidoethyl 28 79-81 Dimethylammenium Iodide. Methyla-Iodopropionate.-- l-Carbomethoxyethyl 2-Aerylamidoethyl 39 90-91-Dimethylammonium Iodide. Methyl Chloroaeetate Carbomethoxymethyl2-Acrylam1doethyl 85 155-156 Diethylammonium Chloride. MethylBromoaeetate Carbomethoxymethyl 2-Aerylam1doethyl 01 14Cr146Diethylarnmonium Bromide. Ethyl Bromoaeetate. Darboethoxymethyl2-Acrylamidoetuyl 54 97-98 Diethylammonium Bromide. Ethyl IodoacetateOarboethoxymethyl 2-Aerylam1doethyl 60 107-107.!

Diethylammonium Iodide.- Methyl Chloroacetate Carhomethoxymethyl3-Aerylam1dopro- 95 149-150 (doe) p Dimethylammonium Chloride.MethylBromon'cetate- Oarbomethoxymethyl 3-Acry1am1dopro- 90 150150.5

pyl Dimethylammomum Bromide. Ethyl Bromoneetate.-. Carboethoxymethyl3-Acrylam1dopropyl 90 1325-133 Dimethylemmoniumjromide. MethylIodoaoetate Carbomethoxymethyl S-Aerylarmdopro- 91 137-138" pylDimethylammonium lodide;

TABLE II-Contlnued Aminoamide Halogenated Ester Betaine DerivativeYield, Melting Percent Point, 0. 3-Acrylamidopropyl dimethylamine Ethyla-Bromopropionate. l-Oarboethoxyethyl 3-Acrylamidopropyl 77 143-144Dimethylammonium Bromide. Do Methyl -Iodoprop1onate l-Carbomethoxyethyl3-Acrylamidopro- 81 117-118 pyl Dlmethylammonium Iodide.

3-Acrylaznidopropyldiethylamme Ethyl Bromoacetate Carboetboxymethyl3-Aerylamidopropy1 98 122-123 Dietbylammonium Bromide. 1

Do Ethyl Iodoacetate Carboethoxymethyl 3-Aerylamidopropyl 75 111-112Diethylammonium Iodide.

Betaines from betaine derivatives described in Example 11 TABLE I I- ntnued A solution of 0.1 molar part of the respective betaine derivativelisted in Table III, dissolved in 100 parts of water is treated with asuflicient quantity of a solution of a base, e. g., NaOH dissolved inwater to cause the pH of the resulting mixed solution to rise to a valueN,3-Methacrylamidopropyl-NN- dimetbylaminoacetate betaine.

Carbpmethoxymethyl 3-Metbacrylamldopropyl Dimethylammonium O hlorideCarboetho xymethyl 3-Metbacryl- Do. between 10.0 and 12.0 and to remainwithin this range alfiidqlmpylDimelhylammonium for a period of at leastone hour. The quantity of Carbofiefiioxymethy] .1v h i aforementionedbase solution required is somewhat more gggf gg than an equimolecularamount of the betaine derivative Carboethdxymethy] 3-Methagry]. Demployed, i. e., in the examples described somewhataBlggfjggopylDimethylammfmium more than 0.1 molar part.Oarbometlioxymethyl 3-VIethacryl- Do.

When a period of about one hour has elapsed since ig gg g the additionof the base solution sutficient dilute aqueous Carboethoxymethyl3-Metl1aoryl- Do.

solution of an acid, e. g., hydrochloric acid, sulfuric ?D(J1i%0pl0py1Dimetbylammonium 0 1 acid, or acetic acid, 1s added to cause the pH ofthe e. l-Oarboethoxyethyl 3 -Methacryl- N,3-Methacrylamidopropyl-N,

mixed solution to be lowered to a value between 6.5 and fgg gg bfimeethyl-aflminopropionflte s 6 am 7.5. There is thus prepared aneutral SOILIUOII of a l-Carbomethoxyethyl 3-Metbacryl- Do.

polymerizable, betaine-containing acrylamide or m-substituted acrylamidelisted in Table III suitable for use directly in making homopolymers andcopolymers or amidopropyl Dimethylammonium Iodide.

Oarbomethuxymethyl 3-Methaeryl- N,3 Methacrylamidopropyl-N amldopropylD1ethylammonium N-diethylaminoacetate be- Bromide. taine.

other compounds. Oarbpethoxymetbyl 3-Methacryl- Do. The betaines may beisolated by a procedure as folgigf f g Dlethylammmmm lows: To theneutral solution of the betaine prepared Carbomethoxymetbyl 3-Methaoryl-Do.

as described above, there is added a suitable polymerii'jff g fDlethylammmum zation inhibitor and the water is evaporated under re-Oarboethoxymethyl 3-Metbacryl- Do.

duced pressure at room temperature. The residue is imaicliopropylDiethylammonium 0 1 8. then dried completely 1n vacuo over a strongdesiccatmg N, 2 Acrylamidoethyl N N-diagent, e. g., phosphorouspentoxide, and extracted with ggfggg Dlmethylammmmm methylammoacetate asuitable solvent, e. g., acetonitrile or dimethylformam-Carbomethoxymethyl 2-Acrylami- Do. ide at a temperature from 40 to 80 C.When this ggg g Dlmethylammmum extract is cooled the crystalline betaineis deposited. Oarboethoxymethyl Z-Acrylamido- Do.

ethyl Dimethylammonium Bro- TABLE III Ct i b hzthoxymethyl 2-Acrylamido-Do.

ethyl Dimethylammonium Iodide. l-Oarbomethoxyethyl 2-AcrylamidoethylDimethylammonium Iodide.

N, 2 Aerylamidoethyl N, N-di- Betaine Derivative taine.Garbomethoxymethyl Z-Acrylamido- N, 2 Acrylamidoetbyl-N, N -diarb y g q:Q' l z D0 ethyl Diethylammonium Chloride. etbylaminoacetate betaine.

amidqothyl Dimethylammomum dunethylaminoacetate betaine.oarbomethoxymethyl2 Acry1amidO Chloride. ethyl Diethylammonium Bromide.car pe y i i' Carboethoxymethyl 2-Acrylamido- Do.

a q y Dlmethylammomllm ethyl Dietbylammonium Bromide. Chloride.Carboethoxymethyl 2-Acrylmnido- D0. carbpme o y e y e ethyl.Diethylammonium Iodide.

amidqethyl Dlmethylammonmm Carbomethoxymethyl 3-Acrylamido- N, 3Acrylamid opropyl N N Bromide. propyl DimetbylammoniumChlodimethylaminoacetate betaine. Oarbpethoxymethyl 2-Methacryl- Do.ride.

fignl qlz yl Dlmethylflmmomum Oarbometjlgoxyngethyl3-Acrylamdo- D0.

romi e. r 0- Oarbomethoxymethyl Z-Methaqryl- Do. 5 yammomum r t mgd oehyl Dlmethylammomum Oarboetllugymeignil 3-Acry1am1i3do- D0.

0 1 6. r0 im ammoni in re- Oarbpethoxymethyl 2-Methacryl- Do. 5 mg? at yu amldoet yl Dlmethylammomum Carbometboxymethyl 3-Acrylamido- Do.

Iodide. l D eth 1a mo ium I0- l-Carboethoxyethyl Z-Methacrylgigg y m nN,2 -Methacrylamidoethyl-N,N- amidoethyl Dimethylamrnonium dimethyl-a-aminopropionate be l-Garlioethoxyethyl 3-Acrylamido- N, 1 1Acrylamidopropyl I I, N Br rd n tame. propyl DimethylamznoniumBrodlmetbyl c: aminopropionate l-Carbomethoxyethyl e-Methaoryb Do. midemama g% Dlmethylammomum l-(lairbomethoxyethyl B-Acrylarni- Do.

N-2-Methacrylamidoethyl-N,N-

dopropyl Dimethyiammonium Iodiethylaminoacetate betaine. dldeOarboethoxymcthyl B-Acrylamido- (larbomethoxymethyl 2-Methacrylamidoethyl Diethylammonium N, 3-Acr lamido 0 l- N N- Ghloride. y prDy Garbomethorymethyl 2Metbacryl Do rgopyl DiethylarnmoniumBrodiethylaminoacetate betaine.

' mi e. fifig gg Dlethylammomum Oarboethoxymethyl S-Acrylamido- Do.Oarboetho xymethyl Z-Methacryl- Do. propyl DlethylammomumIodldeamidogthyl Diethylammonium Bromi e. carbtlmemlxymeihyl qryl- Do.In the practice of th1s invention there may be used fifiggDlethylammomum any N-dialkylaminoalky1arnide of an tat-methylene orgamcg f W Q monocarboxylic acid, preferably aliphatic, and any lacarni oet yle y ammonium Iodide.,.

tone of a B-hydroxy organic monocarboxylic acid, prefergenated organicmonocarboxylic acid, preferably aliphatic, inwhich the halogen ischlorine, bromine, or iodine. In addition to theN-dialkylaminoalkylamides of acrylic acidand a-methyacrylic acid used inthe examples, those of a-ethylacrylic acid, ot-propylacrylic acid,a-isopropylacrylic acid, a-phenylacrylic acid, and a-cyclohexylacrylicacid may be used. In addition to the acrylic or ocsubstituted acrylicamidesofdialkylaminoethylamine and of dialkylaminopropylamine describedin the examples, there may be used those amides of dialkylarninoisopropylamine, -n-butylamine, -n-amylamine, and -n-hexylamine, and inaddition to the dimethylaminoalkylamides and diethylaminoalkylamidesused in the examples and above there may be used the correspondingmethylethylaminoalkylamides, and methyl propylaminoalliylamides.

The N-dialkylaminoalkyl-acrylarnides and tic-substituted acrylamides canbe made by the methods described in U. S. Patents 2,311,548 and2,595,907 and by the method of Helv. Chim. Acta, 34,875 (.1951), inwhich acrylic or an tit-substituted acrylic acid is used as the aminoacid.

In addition to propiolactone given in the examples one may usefl-butyrolactone, fl-isobutyrolactone, fi-valerolactone, etc. Inaddition to the halogenated aliphatic esters given in the examples, onemay use the methyl, ethyl, propyl, isopropyl, and butyl esters ofoz-bromobutyric acid, a-iOdOPIOplOniC acid, ct-iodobutyric acid,iodoacetic acid, oc-chloropropionic acid, a-chlorobutyric acid, etc.

The reaction of the dialk-ylaminoallryl-acrylamides or fl-SllbStltlltCdacrylamideswith a B-lactone or with a halogenated aliphatic ester may becarried out in bulk or in a suitable diluent. The diluent can be aliquid in which the reactants are soluble and to which they are inert,and in which the product is insoluble and to which it is inert, such asdiethylether, dipropylether, diisopropyl ether, ethyl propylether, ethylisopropyl ether, methyl ethyl ether, methyl isopropyl ether, methylpropyl ether, methyl butyl ether, acetone, methyl ethyl ketone, diethylketone, methyl isopropyl ketone, methyl propyl ketone', dioxane,tetrahydrofuran, benzene, toluene, acetonitrile, propionit'rile, etc.

The hydrolysis of the ester group in the aforementioned betainederivatives of the dialkylaminoalkylacrylamides and tat-substitutedacrylamides may be carried out not only in water as a single solvent butalso in mixtures of water with water-miscible organic solvents such asmethanol, ethanol, propanol, isopropyl alcohol, tert-butyl alcohol,acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, dioxane,etc. Furthermore, during the operation of this reaction theconcentration of the betaine derivative may be varied over a very widerange, the exact concentration to be chosen depending on the use towhich the product of said reaction is to be put.

Suitable bases for the promotion of this hydrolysis are sodiumhydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide,barium hydroxide, strontium hydroxide, calcium hydroxide, ammoniumhydroxide, etc., and certain of the quaternary ammonium hydroxides andorganic amines, e. g., tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, piperidine, cyclohexylamine, triethylamine, andtrimethylamine.

The temperature of this hydrolysis reaction may be any convenienttemperature provided polymerization inhibitors are present but. is moresatisfactorily room temperature. The time required for completion ofthis hydrolysis varies with the reactivities of the compounds involvedand can be followed exactly by adding the base slowly and makingconcurrent measurements of the PH of the solution. Additions of basegive immediate increases in the pH of the solution. Up until the time ofcompletion of the hydrolysis-reaction the pH will drift back to lowervalues. When the reaction is complete the pH will cease to driftdownward and will remain at its initial high. value produced by theaddition of alkali.

When the hydrolysis reaction. is complete, acid may or may not be usedto neutralize the resulting solution, de-

pending, on the use to which it is to be put. If acid is used it. may beany of the. common. organic or inorganic acids such as hydrochloricacid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid,trichloracetic acid, chloroacetic acid, acetic acid, propionic acid, p-'

toluene-sulfonicacid, benzene sulfonic acid, methanesulfonic acid,carbonic acid, etc.

In order for the aforementioned betaine derivatives to be useful in thepreparation of homopolymers and co polymers containing the betaine groupit is not necessary that the hydrolysis of the ester groups in theaforementioned derivatives be carried out before polymerization.

Moreover, homopolyrners and copolymers can be made equally well from theester derivatives and the hydrolysis of the ester group carried out onthe resulting homopolymers or copolymers. The choice as to whether tohydrolyze the ester group in the. aforementioned betaine derivativesbefore or after polymerization or copolymerization will depend uponconsiderations of convenience in the particular case to be employed.Equally satisfactory polymers are obtained by both procedures.

The betaine-containing and betaine derivative-containing polymerizableamides may also be made by treatment of suitable polymerizable esterswith suitable betaine-containing or betaine derivative-containingamines.

The betaine-containing and betaine derivative-containing. polymerizableamides of this invention find their chief uses in the preparation ofaddition copolymers which can be made by organic solvent or aqueouspolymerization in the manners described in U. S. Patents 1,933,052,2,064,565 and 2,160,938. They are also useful in the preparation of manyother types of polymers, particularly copolymers because of theirability to confer water-solubility over the entire useful pH range onmany polymers which would otherwise be water-insoluble; Amongsuchcopolymers are those obtainable by copolymerizing the above-describedbetaine-containing amides or their derivatives with such polymerizablecompounds, as, for example, esters of acrylic and substituted acrylicacids, vinyl esters, vinyl halides, vinylidene halides, styrene, allylhalides, allyl esters, N-acyl allylamine derivatives, esters of maleic,fumaric, aconitic, itaconic, and citraconic acids, etc. They are alsouseful intermediates in the preparation of other valuable organicchemical compounds. For example, they are useful intermediates in thepreparation of substances with physiological activity, surface-activeagents, humectants and buifers. The compounds may also be used ashalogen acceptors and as intermediates in the preparation ofwater-soluble dyestuffs.

The compounds which are the subject of this application have numerousadvantages. They are easy to prepare in a state of high purity. Thematerials needed for their preparation are available and relativelyinexpensive. Still other advantages will be apparent from the abovedescription of the invention.

The invention claimed is:

l. The compounds of the general formula:

R: R3 l I CHe='C-CONH-Rl-I\iCHa-CHR"-GQO wherein R is a member takenfrom the group consisting of hydrogen, alkyl radicals of 1 to 3 carbonatoms, phenyl and cyclohexyl, R1 is a saturated aliphatic hydrore-macarbon radical of 1 to 6 carbon atoms, R2 is an alkyl radical of 1 to 3carbon atoms, R3 is an alkyl radical of wherein R is a member taken fromthe group consisting of hydrogen, alkyl radicals of 1 to 3 carbon atoms,

phenyl and cyclohexyl, R1 is a saturated aliphatic hydrocarbon radicalof 1 to 6 carbon atoms, R2 is an alkyl radical of 1 to 3 carbon atoms,R3 is an alkyl radical of l to 3 carbon atoms, and R1 is a member takenfrom the group consisting of hydrogen and alkyl radicals of 1 to 2carbon atoms.

4. The compounds of the general formula:

wherein R2 is an alkyl radical of 1 to 3 carbon atoms, R3 is an alkylradical of 1 to 3 carbon atoms, R4 is a member taken from the groupconsisting of hydrogen and alkyl radicals of 1 to 2 carbon atoms, and nis a positive integer from 1 to 6.

5. The compounds of the general formula:

wherein R2 is an alkyl radical of 1 to 3 carbon atoms, R: is an alkylradical of 1 to 3 carbon atoms, R4 is a member taken from the groupconsisting of hydrogen and alkyl radicals of 1 to 2 carbon atoms, and nis a positive integer from 1 to 6.

6. The compounds of the general formula:

at OH1=GOONH-(OHz)n-N CH1OHRC0O- wherein R2 is an alkyl radical of 1 to3 carbon atoms, h is an alkyl radical of 1 to 3 carbon atoms, R" is amember taken from the group consisting of hydrogen and alkyl radicals of1 to 2 carbon atoms, and n is a positive integer from 1 to 6.

7. The compounds of the general formula:

(IJHs R2\ 1113 CH2=OCONH(OH1),.N -CH:CHRCO- wherein R2 is an alkylradical of 1 to 3 carbon atoms, R3 is an alkyl radical of 1 to 3 carbonatoms, R" is a member taken from the group consisting of hydrogen andalkyl radicals of 1 to 2 carbon atoms, and n is a positive integer from1 to 6.

8. The compounds of the general formula:

wherein R is a member taken from the group consisting of hydrogen, alkylradicals of 1 to 3 carbon atoms, R1 is a saturated aliphatic hydrocarbonradical of 1 to 6 carbon atoms, R2 is an alkyl radical of 1 to 3 carbonatoms, R3 is an alkyl radical of 1 to 3 carbon atoms, R5 is an alkylradical of 1 to 4 carbon atoms, and R is a saturated aliphatichydrocarbon radical of 2 to 4 carbon atoms, and X is a halogen takenfrom the group consisting of chlorine, bromine and iodine.

9. The compounds of the general formula:

10 wherein R is a member taken from the group consisting of hydrogen,alkyl radicals of 1 to 3 carbon atoms, R1 is a saturated aliphatichydrocarbon radical of 1 to 6 carbon atoms, R2 is an alkyl radical of 1to 3 carbon atoms, R3 is analkyl radical of 1 to 3 carbon atoms, R4 is amember taken from the group consisting of hydrogen and alkyl radicals of1 to 3 carbon atoms, and R5 is an alkyl radical of 1 to 4 carbon atoms,and X is a halogen taken from the group consisting of chlorine, bromineand iodine.

10. N,3 methacrylamidopropyl N,N dimethyl p-aminopropionate betaine.

11. N,2 methacrylamidoethyl N,N dimethyl B aminopropionate betaine.

12. N,3 acrylamidopropyl N,N dimethyl 3 aminopropionate betaine.

13. N,2 acrylamidoethyl N,N dimethyl B aminopropionate betaine.

14. The process which comprises reacting a dialkylaminoalkylacrylamidehaving the general formula:

wherein R is a member taken from the group consisting of hydrogen, alkylradicals of 1 to 3 carbon atoms, phenyl and cyclohexyl, R1 is asaturated aliphatic hydrocarbon radical of 1 to 6 carbon atoms, R2 is analkyl radical of 1 to 3 carbon atoms and R3 is an alkyl radical of 1 to3 carbon atoms, with a fl-lactone in the presence of an inert liquiddiluent at a temperature from 20 C. to +40 C. and in the substantialabsence of water.

15. The process which comprises reacting a dialkylaminoalkylacrylamidehaving the general formula:

wherein R is a member taken from the group consisting of hydrogen, alkylradicals of 1 to 3 carbon atoms, phenyl and cyclohexyl, R1 is asaturated aliphatic hydrocarbon radical of 1 to 6 carbon atoms, R2 is analkyl radical of 1 to 3 carbon atoms and R3 is an alkyl radical of 1 to3 carbon atoms with a lower alkyl ester of a monohalogen-substitutedfatty acid in the presence of an inert liquid diluent at a temperatureof 20 C. to +60 C.

16. The process which comprises reacting a dialkylaminoalkylacrylamidehaving the general formula:

wherein R is a member taken from the group consisting of hydrogen, alkylradicals of 1 to 3 carbon atoms, phenyl and cyclohexyl, R1 is asaturated aliphatic hydrocarbon radical of 1 to 6 carbon atoms, R2 is analkyl radical of 1 to 3 carbon atoms and R3 is an alkyl radical of 1 to3 carbon atoms with a lower alkyl ester of a monohalogen-substitutedfatty acid in the presence of an inert liquid diluent at a temperatureof 20 C. to +40 C. and hydrolyzing the resulting alkyl ester.

17. The process which comprises reacting a dialkylaminoalkylacrylamidehaving the general formula:

wherein R is a member taken from the group consisting of hydrogen, alkylradicals of 1 to 3 carbon atoms, phenyl and cyclohexyl, R1 is asaturated aliphatic hydrocarbon radical of 1 to 6 carbon atoms, R2 is analkyl radical of 1 to 3 carbon atoms and R3 is an alkyl rad- 11 icalot-v 1 to 3 carbon atoms with a lower alkyl ester. of ana-monohalogen-substituted fatty acid in the presence of an. inert liquiddiluent at a temperature of 20 C. to +60 C. and hydrolyzing theresulting alkyl esterc 18'. The process which comprises reacting adialkylaminoalkylacrylamide having the general formula:

R /Ra CHa= il-*C ONHRiN wherein R is a member taken from the groupconsisting of hydrogen, alkyl radicals of 1 to 3 carbon atoms, phenyland cyclohexyl, R1 is a saturated aliphatic hydrocarbon radical of 1 to6 carbon atoms, R2 is an alkyl radical of 1 to 3 carbon atoms and'Ra isan alkyl radical of 1 to 3 carbon atoms with a lower. alkyl ester of anot-monohalogen-substituted fatty acid of 2 to 5' carbon atoms in thepresence of an inert liquid diluent at a temperature of 20 C. to +60 C.,hydrolyzing the resulting betaine derivative in an aqueous alkaline so-20 lution and neutralizing said solution to a value between pH 6.5 and7.5.

12 19. An, aqueous solution having a pH between 6.5 and 'LS obtainedby'alkaline hydrolysis of the betaine derivative defined in claim 9andcontaining a betaine compound of the. general formula:

R Ra\1|i'.a o-HFo-c 6NH-R1-N (JHO o 0 7 B4 wherein R is a member takenfrom the group consisting of hydrogen, alkyl radicals of 1 to 3 carbonatoms, phenyl and cyclohexyl, R1 is a saturated aliphatic hydrocarbonradical of 1 to 6 carbon atoms, R2 is an alkyl radical of 1 to 3 carbonatoms, R3 is an alkyl radical of 1 to 3 carbon atoms, and R4 is a membertaken from the group consisting of hydrogen and alkyl radicals of 1 to 2carbon. atomsand salts of neutralization.

References Cited in-the fileof this patent UNITED STATES PATENTS

1. THE COMPOUND OF THE GENERAL FORMULA:
 8. THE COMPOUNDS OF THE GENERALFORMULA: